CA2008925C - Ionomer composition - Google Patents
Ionomer compositionInfo
- Publication number
- CA2008925C CA2008925C CA002008925A CA2008925A CA2008925C CA 2008925 C CA2008925 C CA 2008925C CA 002008925 A CA002008925 A CA 002008925A CA 2008925 A CA2008925 A CA 2008925A CA 2008925 C CA2008925 C CA 2008925C
- Authority
- CA
- Canada
- Prior art keywords
- weight
- ethylene
- parts
- olefin
- ionomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
- C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
- C08L23/0876—Salts thereof, i.e. ionomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
- C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
- C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
- C08L23/0884—Epoxide-containing esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
Proposed herein is an ionomer composition which comprises a reaction product of from 90 to 99.5 % by weight of an ethylene copolymer ionomer (A) comprising ethylene units and unsaturated carboxylic acid salt units with from 0.5 to 10% by weight of an olefin copolymer (B) having epoxy groups in its side chains, and from 5 to 200 parts by weight, based on 100 parts by weight of the reaction product, of an olefin thermoplastic elastomer (C) comprising an ethylene .alpha.-olefin copolymer rubber (a) and a polyolefin resin (b), at least one of (a) and (b) being partly crosslinked. The proposed ionomer composition is excellent in scratch resistance and flexibility and exhibits a reduced "luster reappearance".
Description
IONOMER COMI'OSITION 2QC~925 Field of the Invention The present invention relates to an ionomer composi-tion which is excellent in scratch resistance, impactstrength, heat resistance and flexibility. More particu-larly, it relates to an ionomer composition comprising a reaction product of an ethylene copolymer-type ionomer,which may be referred to herein briefly as an ionomer, with an olefin copolymer having epoxy groups in its side chains, and an olefin-type thermoplastic elas-tomer.
Prior Art Because ionomer resins are light in weight and rigid, and are excellent in scratch resistance and impact strength at cold atmospheric temperatures, they draw attention of the art as attractive resins for use in automotive exteri-ors.
In some applications, including automotive interiors such as materials for lining doors, further improvements of the ionomer resins in flexibility and heat resistance are desired in the art, while enjoying their advantageous prop-erties such as excellent scratch resistance and impactstrength at cold atmospheric temperature. The heat resis-tance required for materials used in such applications in-cludes, in addition to usual resistance to heat deforma-tion, such a property that the surfaces of the materials do Z~ 925 not cause a phenomenon called "luster reappearance" due to heat. Generally, surfaces of lining materials are delus-tered by embossing. However, it is frequently observed that when an embossed lining material is subjected to an elevated temperature as high as 120 ~C., which is the sup-posed highest temperature inside automobiles, it melts due to heat whereby the surface of the material may lose the emboss to become smooth and reappearance luster before the embossing. This phenomenon is called "luster reappear-ance". Thus, materials for use in lining automotive doorsare required that they are not suffered from "luster reap-pearance".
In applications where scratch resistance is of paramount importance, it is necessary to use such ionomer resins that they contain increased amounts of metallic ions. The higher the metallic ion content becomes, how-ever, ionomer resins tend to become more rigid and more lustrous. It is not easy to make such ionomer resins delustrous by embossing. It is therefore desired to pro-vide ionomer resins which are excellent in flexibility as well as scratch resistance.
Our Japanese Patent Laid-open Publication No. 61-363~7 discloses a polymer composition having excellent scratch resistance and heat deformation resistance comprising an ionomer and an olefin-type thermoplastic elastomer. While the proposed polymer composition is excellent in resistance 20~925 to heat deformation, it is insufficient in respect of the above-mentioned "luster reappearance".
Japanese Patent Laid-open Publication No. 63-165448 discloses and claims a resin composition having an improved impact resistance comprising (a) from 5 to 95 parts by weight of a resin having at least one epoxy group in its molecule and a flexural modulus of not more than 10,000 kg/cm2 at room temperature melt blended with (b) from 95 to 5 parts by weight of a copolymer of an ~-olefin and an ~, ~-unsaturated carboxylic acid having at least 5 mol % of its carboxyl groups neutralized with an alkali metal salt and a flexural modulus of not more than 10,000 kg/cm2 at room temperature.
Object of the Invention In view of the state of the art discussed above, an object of the invention is to provide an ionomer composition which is excellent in scratch resistance and flexibility and exhibits a reduced "luster reappearance".
Accordingly, the invention provides an ionomer composition which comprises a reaction product of from 90 to 99.5 % by weight of an ethylene copolymer ionomer (A) comprising ethylene units and unsaturated carboxylic acid salt units with from 0.5 to 10% by weight of an olefin copolymer (B) having epoxy groups in its side chains, and from 5 to 200 parts by weight, based on 100 parts by weight of the reaction product, of an olefin thermoplastic elastomer (C) comprising an ethylene ~-olefin copolymer rubber (a) and a polyolefin resin (b), at least one of (a) and (b) being partly cross-~' in:jj 3alinked.
De~cription of the Invention It has now been found that an ionomer composition having a well-balanced combination of the desired properties can be obtained by reacting an ethylene copolymer-type ionomer with an olefin copolymer having epoxy groups in its side chains, and incorporating the resulting reaction product with an olefin-type thermoplastic elastomer.
~ . ..
~ ln:~
Z~R92S
Thus, the invention provides an ionomer composition which comprises a reaction product of from 90 to 99.5 ~ by weight of an ethylene copolymer-type ionomer (A) with from 0.5 to 10 ~ by weight of an olefin copolymer (B) having epoxy groups in its side chains, and from 5 to 200 parts by weight, based on 100 parts by weight of said reaction prod-uct, of an olefin-type thermoplastic elastomer (C).
The ionomer composition according to the invention 0 will now be described in detail.
The ethylene copolymer-type ionomer (A) used herein comprises ethylene units and unsaturated carboxylic acid salt units as essential polymer constituent units, and op-tionally contains unsaturated acid units, unsaturated acidester units and other comonomer units. Such an ionomer (A) may be prepared either from an ethylene-unsaturated car-boxylic acid copolymer comprising ethylene units, unsatu-rated carboxylic acid units and optionally other comonomer units by neutralizing at least a part of its unsaturated carboxylic acid units with a metallic ion and/or an organic amine, or from an ethylene-unsaturated carboxylic acid ester copolymer comprising ethylene units, carboxylic acid ester units and optionally other comonomer units by saponi-fying at least a part of its unsaturated acid ester units.
In the starting ethylene-carboxylic acid copolymer comprising ethylene units, unsaturated carboxylic acid units and optionally other comonomer units, the unsaturated 2~89~5 carboxylic acid units are derived from at least one unsatu-rated carboxylic acid preferably having from 3 to 8 carbon atoms. Examples of such an unsaturated carboxylic acid, include, for example, acrylic acid, methacrylic acid, fu-maric acid, itaconic acid, maleic anhydride, monomethylmaleate and monoethyl maleate. Of these, preferred are acrylic acid, methacrylic acid and maleic anhydride. The unsaturated carboxylic acids may be incorporated in the copolymer by either random or graft copolymerization. From the stand point of transparency of the ionomer, they are preferably random copolymerized. The optional third comonomer units may be derived from at least one other comonomer. Examples of such a third comonomer include esters of unsaturated carboxylic acids such as methyl acry-late, ethyl acrylate isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate and methyl methacrylate, and alkenyl esters of saturated carboxylic acids such as vinyl acetate.
The ethylene-unsaturated carboxylic acid copolymers for use in the preparation of the ethylene copolymer-type ionomer (A) used herein desirably comprise from 40 to 99 %
by weight, preferably from 50 to 98 ~ by weight, of the ethylene units and from 1 to 50 % by weight, preferably from 2 to 40 % by weight, of the unsaturated carboxylic acid units. When the starting ethylene-unsaturated acid copolymer contains the third comonomer units, they should be present in the copolymer in an amount of not exceeding 50 % by weight, preferably not exceeding 40 % by weight.
Z~C~925 The starting ethylene-unsaturated carboxylic acid copolymer is at least partly neutralized with metallic ca-tions having a valency of from 1 to 3 and/or organic amines to provide the ethylene copolymer-type ionomer (A) which can be used herein. Examples of the usable metallic ca-tions include, for example, Na+, K+, Li+, Ca++, Mg++, Zn++, Cu++, Co++, Ni++, Mn++ and Al+++. F,xamples of usable or-ganic amines include, for example, n-hexylamine, hexam-ethylenediamine, 1,3-bisaminomethylcyclohexane and m-xylenediamine. The neutralization result in the formationof carboxylic acid salt units, which will act as a catalyst for the reaction between the carboxylic groups of the ionomer (A) and epoxy groups of the olefin copolymer (B) having epoxy groups in its side chains. In the absence of the carboxylic acid salt units, the reaction tends to un-evenly proceed so that marked improvements in mechanical properties of the reaction product at elevated temperatures will not be achieved. The neutralizing agents may be used alone or in combination.
Preferred ionomers which can be used herein may be ob-tained by preparing a copolymer of ethylene, at least one unsaturated carboxylic acid and optionally one or more third comonomer by a high pressure radical polymerization process, and neutralizing at least a part, normally from 5 to 95 %, preferably from 10 to 90 % of carboxyl groups of the copolymer with metallic cations. Preferred ionomers which can be used herein generally have a melting point within the range between 70 and 105 ~C. and a melt flow Z~9~
rate (MFR) of from 0.01 to 1000 g/10 min, in particular from 0.1 to 200 g/ 10 min, measured at a temperature of 190 ~C. and under a load of 2160 g.
As the olefin copolymer (B) having epoxy groups in its side chains particularly preferred are copolymers of at least one a-olefin with at least one ethylenically unsatu-rated glycidyl compound selected from glycidyl acrylate, glycidyl methacrylate and ethylenically unsaturated gly-cidyl ethers. Preferred a-olefins are those having from 2 to 8 carbon atoms such as ethylene, propylene and butene-1.
Examples of the ethylenically unsaturated glycidyl ethers include, for example, glycidyl vinyl ether, allyl glycidyl ether and methallyl glycidyl ether.
In addition to a-olefin units and epoxy group-con-taining comonomer units, the olefin copolymer (B) may con-tain third comonomer units. Suitable third comonomers are those illustrated hereinabove in respect of the third comonomer of the ethylene-unsaturated carboxylic acid copolymer which is a starting material for the preparation of the ionomer (A), and include esters of unsaturated car-boxylic acids and alkenyl esters of saturated carboxylic acids. Olefin copolymers (B) containing the third comonomer units may provide crosslinked ionomers having better transparency.
Preferred olefin copolymers which can be used herein comprise from 40 to 99 % by weight, preferably from 50 to 98 % by weight, of the a-olefin units, from 0.5 to 20 % by Z~925 weight, preferably from 1 to 15 % by weight of the glycidyl group-containing comonomer units and from 0 to 49.5 % by weight, preferably from 0 to 40 % by weight of the third comonomer units. With olefin copolymers having unduly low content of the glycidyl group-containing comonomer unit:s, the crosslinked ionomers, and in turn the final ionomer compositions, do not exhibit a satisfactorily reduced "luster reappearance" due to heat. Whereas olefin copoly-mers having excessively high content of the glycidyl group-containing comonomer units result in uneven crosslinking.Accordingly, the content of the glycidyl group-containing comonomer units in the olefin copolymer (B) should be desirably adjusted within the range prescribed above.
While the olefin copolymer (B) having epoxy groups in its side chains which can be used herein may be a random, block or graft copolymer, the random copolymer is preferred since it provides even crosslinking of the ionomer (A).
Such a copolymer can be prepared by a random polymerization process under conditions including, for example, a pressure of from 500 to 3000 kg/cm2 and a temperature of from 150 to 280 ~C.
Olefin copolymers wherein the ~-olefin is ethylene preferably have a melt flow rate of from 0.01 to 1000 g/10 min, in particular from 0.1 to 200 g/10 min, as measured at a temperature of 190 ~C. and under a load of 2160 g.
9 2~9~:5 The mechanism of the reaction between the ionomer (A) and the olefin copolymer (B) having epoxy groups in its side chains is supposed such that the carboxyl groups in the ionomer (A) react with the epoxy groups in side chains 5 of the olefin copolymer (B) to form a crosslinked reaction product in which polymer chains of the ionomer are cova-lently connected via molecules of the olefin copolymer.
Upon this reaction the carboxylic acid salt units in the ionomer appear to act as a catalyst. In this reaction no by-products such as water and gases are formed, and thus foaming due to by-products is not observed.
The reaction between the ionomer (A) and the olefin copolymer (B) is conveniently carried out by melt blending the reactants. While the reaction may be carried out in so-lution by dissolving and bringing the reactants in contact to each other in an appropriate solvent, this solution pro-cess requlres a relatively long reaction time and an addi-tional step of solvent removal. Accordingly, we prefer to the melt blending process. The melt blending may be car-ried out in a melt mixer or processing apparatus for ther-moplastic resins at a temperature of from 100 to 300 ~C., preferably from 150 to 280 ~C.
The proportions of the reactants used in the prepara-tion of the crosslinked ionomer are from 90 to 99.5 % by weight, preferably from 92 to 99 % by weight, of the ionomer (A) to from 0.5 to 10 % by weight, preferably from 1 to 8 ~ by weight, of the olefin copolymer (B) having 1 o 2~9~5 epoxy groups in its side chains. With substantially less than 0.5 % by weight of the olefin copolymer (B) having epoxy groups in its side chains based on the total weight of the ionomer (A) and olefin copolymer (B), no appreciable reduction in "luster reappearance" of the crosslinked ionomer, and in turn the final ionomer composition, will be achieved. Whereas use of the olefin copolymer (B) substan-tially in excess of 10 % by weight based on the total weight of the ionomer (A) and olefin copolymer (B) will re-sult in excessive crosslinking, leading to a remarkable re-duction in flowability and moldability of the crosslinked ionomer, and in turn the final ionomer composition.
The olefin-type thermoplastic elastomer (C) used herein comprises an ethylene-a-olefin copolymer rubber (a) and a polyolefin resin (b) as essential ingredients, with the proviso that at least one of the ingredients (a) and (b), normally the ethylene-a-olefin copolymer rubber (a), is partly crosslinked.
The olefin-type thermoplastic elastomer (C) can be a partly crosslinked rubber composition (I) obtained by partly crosslinking a mixture of the ethylene-a-olefin copolymer rubber (a) and the polyolefin resin (b); or a composition obtained by adding a further polyolefin resin (II) to the partly crosslinked rubber composition (I) above; or a composition obtained by adding the polyolefin resin (II) to a a partly crosslinked ethylene-a-olefin copolymer rubber. The material to be partly crosslinked, 1 1 ZOC~39~5 that is the ethylene-a-olefin copolymer rubber or the mix-ture of the ethylene-a-olefin copolymer rubber (a) and the polyolefin resin (b) may be incorporated with a peroxide-noncrosslinkable hydrocarbon rubber (c) and/or a mineral oil softener (d).
More particularly, examples of the olefin-type thermo-plastic elastomer (C) include:
(1) a thermoplastic elastomer composition (I) obtained 0 by dynamic heat treatment of a mixture comprising:
(a) from 20 to 95 parts by weight, preferably from 80 to 30 parts be weight, of an ethylene-a-olefin copolymer rubber, (b) from 5 to 80 parts by weight, preferably from 20 to 70 parts by weight, of a polyolefin resin, and option-ally from 0 to.100 parts by weight,preferably from 5 to 80 parts by weight, based on 100 parts by weight of the total weight of the (a) ~ (b), of at least one component selecled from (c) peroxide-noncrosslinkable hydrocarbon rubbers and (d) mineral oil softeners in the presence of a crosslinking agent;
(2) a composition comprising 30 parts by weight of the thermoplastic elastomer composition (I) above and up to 70 parts by weight of a polyolefin resin (II), the total weight of (b) and [II] in the final composition being up to 12 2~3925 80 parts by weight based on 100 parts by weight of the com-position;
Prior Art Because ionomer resins are light in weight and rigid, and are excellent in scratch resistance and impact strength at cold atmospheric temperatures, they draw attention of the art as attractive resins for use in automotive exteri-ors.
In some applications, including automotive interiors such as materials for lining doors, further improvements of the ionomer resins in flexibility and heat resistance are desired in the art, while enjoying their advantageous prop-erties such as excellent scratch resistance and impactstrength at cold atmospheric temperature. The heat resis-tance required for materials used in such applications in-cludes, in addition to usual resistance to heat deforma-tion, such a property that the surfaces of the materials do Z~ 925 not cause a phenomenon called "luster reappearance" due to heat. Generally, surfaces of lining materials are delus-tered by embossing. However, it is frequently observed that when an embossed lining material is subjected to an elevated temperature as high as 120 ~C., which is the sup-posed highest temperature inside automobiles, it melts due to heat whereby the surface of the material may lose the emboss to become smooth and reappearance luster before the embossing. This phenomenon is called "luster reappear-ance". Thus, materials for use in lining automotive doorsare required that they are not suffered from "luster reap-pearance".
In applications where scratch resistance is of paramount importance, it is necessary to use such ionomer resins that they contain increased amounts of metallic ions. The higher the metallic ion content becomes, how-ever, ionomer resins tend to become more rigid and more lustrous. It is not easy to make such ionomer resins delustrous by embossing. It is therefore desired to pro-vide ionomer resins which are excellent in flexibility as well as scratch resistance.
Our Japanese Patent Laid-open Publication No. 61-363~7 discloses a polymer composition having excellent scratch resistance and heat deformation resistance comprising an ionomer and an olefin-type thermoplastic elastomer. While the proposed polymer composition is excellent in resistance 20~925 to heat deformation, it is insufficient in respect of the above-mentioned "luster reappearance".
Japanese Patent Laid-open Publication No. 63-165448 discloses and claims a resin composition having an improved impact resistance comprising (a) from 5 to 95 parts by weight of a resin having at least one epoxy group in its molecule and a flexural modulus of not more than 10,000 kg/cm2 at room temperature melt blended with (b) from 95 to 5 parts by weight of a copolymer of an ~-olefin and an ~, ~-unsaturated carboxylic acid having at least 5 mol % of its carboxyl groups neutralized with an alkali metal salt and a flexural modulus of not more than 10,000 kg/cm2 at room temperature.
Object of the Invention In view of the state of the art discussed above, an object of the invention is to provide an ionomer composition which is excellent in scratch resistance and flexibility and exhibits a reduced "luster reappearance".
Accordingly, the invention provides an ionomer composition which comprises a reaction product of from 90 to 99.5 % by weight of an ethylene copolymer ionomer (A) comprising ethylene units and unsaturated carboxylic acid salt units with from 0.5 to 10% by weight of an olefin copolymer (B) having epoxy groups in its side chains, and from 5 to 200 parts by weight, based on 100 parts by weight of the reaction product, of an olefin thermoplastic elastomer (C) comprising an ethylene ~-olefin copolymer rubber (a) and a polyolefin resin (b), at least one of (a) and (b) being partly cross-~' in:jj 3alinked.
De~cription of the Invention It has now been found that an ionomer composition having a well-balanced combination of the desired properties can be obtained by reacting an ethylene copolymer-type ionomer with an olefin copolymer having epoxy groups in its side chains, and incorporating the resulting reaction product with an olefin-type thermoplastic elastomer.
~ . ..
~ ln:~
Z~R92S
Thus, the invention provides an ionomer composition which comprises a reaction product of from 90 to 99.5 ~ by weight of an ethylene copolymer-type ionomer (A) with from 0.5 to 10 ~ by weight of an olefin copolymer (B) having epoxy groups in its side chains, and from 5 to 200 parts by weight, based on 100 parts by weight of said reaction prod-uct, of an olefin-type thermoplastic elastomer (C).
The ionomer composition according to the invention 0 will now be described in detail.
The ethylene copolymer-type ionomer (A) used herein comprises ethylene units and unsaturated carboxylic acid salt units as essential polymer constituent units, and op-tionally contains unsaturated acid units, unsaturated acidester units and other comonomer units. Such an ionomer (A) may be prepared either from an ethylene-unsaturated car-boxylic acid copolymer comprising ethylene units, unsatu-rated carboxylic acid units and optionally other comonomer units by neutralizing at least a part of its unsaturated carboxylic acid units with a metallic ion and/or an organic amine, or from an ethylene-unsaturated carboxylic acid ester copolymer comprising ethylene units, carboxylic acid ester units and optionally other comonomer units by saponi-fying at least a part of its unsaturated acid ester units.
In the starting ethylene-carboxylic acid copolymer comprising ethylene units, unsaturated carboxylic acid units and optionally other comonomer units, the unsaturated 2~89~5 carboxylic acid units are derived from at least one unsatu-rated carboxylic acid preferably having from 3 to 8 carbon atoms. Examples of such an unsaturated carboxylic acid, include, for example, acrylic acid, methacrylic acid, fu-maric acid, itaconic acid, maleic anhydride, monomethylmaleate and monoethyl maleate. Of these, preferred are acrylic acid, methacrylic acid and maleic anhydride. The unsaturated carboxylic acids may be incorporated in the copolymer by either random or graft copolymerization. From the stand point of transparency of the ionomer, they are preferably random copolymerized. The optional third comonomer units may be derived from at least one other comonomer. Examples of such a third comonomer include esters of unsaturated carboxylic acids such as methyl acry-late, ethyl acrylate isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate and methyl methacrylate, and alkenyl esters of saturated carboxylic acids such as vinyl acetate.
The ethylene-unsaturated carboxylic acid copolymers for use in the preparation of the ethylene copolymer-type ionomer (A) used herein desirably comprise from 40 to 99 %
by weight, preferably from 50 to 98 ~ by weight, of the ethylene units and from 1 to 50 % by weight, preferably from 2 to 40 % by weight, of the unsaturated carboxylic acid units. When the starting ethylene-unsaturated acid copolymer contains the third comonomer units, they should be present in the copolymer in an amount of not exceeding 50 % by weight, preferably not exceeding 40 % by weight.
Z~C~925 The starting ethylene-unsaturated carboxylic acid copolymer is at least partly neutralized with metallic ca-tions having a valency of from 1 to 3 and/or organic amines to provide the ethylene copolymer-type ionomer (A) which can be used herein. Examples of the usable metallic ca-tions include, for example, Na+, K+, Li+, Ca++, Mg++, Zn++, Cu++, Co++, Ni++, Mn++ and Al+++. F,xamples of usable or-ganic amines include, for example, n-hexylamine, hexam-ethylenediamine, 1,3-bisaminomethylcyclohexane and m-xylenediamine. The neutralization result in the formationof carboxylic acid salt units, which will act as a catalyst for the reaction between the carboxylic groups of the ionomer (A) and epoxy groups of the olefin copolymer (B) having epoxy groups in its side chains. In the absence of the carboxylic acid salt units, the reaction tends to un-evenly proceed so that marked improvements in mechanical properties of the reaction product at elevated temperatures will not be achieved. The neutralizing agents may be used alone or in combination.
Preferred ionomers which can be used herein may be ob-tained by preparing a copolymer of ethylene, at least one unsaturated carboxylic acid and optionally one or more third comonomer by a high pressure radical polymerization process, and neutralizing at least a part, normally from 5 to 95 %, preferably from 10 to 90 % of carboxyl groups of the copolymer with metallic cations. Preferred ionomers which can be used herein generally have a melting point within the range between 70 and 105 ~C. and a melt flow Z~9~
rate (MFR) of from 0.01 to 1000 g/10 min, in particular from 0.1 to 200 g/ 10 min, measured at a temperature of 190 ~C. and under a load of 2160 g.
As the olefin copolymer (B) having epoxy groups in its side chains particularly preferred are copolymers of at least one a-olefin with at least one ethylenically unsatu-rated glycidyl compound selected from glycidyl acrylate, glycidyl methacrylate and ethylenically unsaturated gly-cidyl ethers. Preferred a-olefins are those having from 2 to 8 carbon atoms such as ethylene, propylene and butene-1.
Examples of the ethylenically unsaturated glycidyl ethers include, for example, glycidyl vinyl ether, allyl glycidyl ether and methallyl glycidyl ether.
In addition to a-olefin units and epoxy group-con-taining comonomer units, the olefin copolymer (B) may con-tain third comonomer units. Suitable third comonomers are those illustrated hereinabove in respect of the third comonomer of the ethylene-unsaturated carboxylic acid copolymer which is a starting material for the preparation of the ionomer (A), and include esters of unsaturated car-boxylic acids and alkenyl esters of saturated carboxylic acids. Olefin copolymers (B) containing the third comonomer units may provide crosslinked ionomers having better transparency.
Preferred olefin copolymers which can be used herein comprise from 40 to 99 % by weight, preferably from 50 to 98 % by weight, of the a-olefin units, from 0.5 to 20 % by Z~925 weight, preferably from 1 to 15 % by weight of the glycidyl group-containing comonomer units and from 0 to 49.5 % by weight, preferably from 0 to 40 % by weight of the third comonomer units. With olefin copolymers having unduly low content of the glycidyl group-containing comonomer unit:s, the crosslinked ionomers, and in turn the final ionomer compositions, do not exhibit a satisfactorily reduced "luster reappearance" due to heat. Whereas olefin copoly-mers having excessively high content of the glycidyl group-containing comonomer units result in uneven crosslinking.Accordingly, the content of the glycidyl group-containing comonomer units in the olefin copolymer (B) should be desirably adjusted within the range prescribed above.
While the olefin copolymer (B) having epoxy groups in its side chains which can be used herein may be a random, block or graft copolymer, the random copolymer is preferred since it provides even crosslinking of the ionomer (A).
Such a copolymer can be prepared by a random polymerization process under conditions including, for example, a pressure of from 500 to 3000 kg/cm2 and a temperature of from 150 to 280 ~C.
Olefin copolymers wherein the ~-olefin is ethylene preferably have a melt flow rate of from 0.01 to 1000 g/10 min, in particular from 0.1 to 200 g/10 min, as measured at a temperature of 190 ~C. and under a load of 2160 g.
9 2~9~:5 The mechanism of the reaction between the ionomer (A) and the olefin copolymer (B) having epoxy groups in its side chains is supposed such that the carboxyl groups in the ionomer (A) react with the epoxy groups in side chains 5 of the olefin copolymer (B) to form a crosslinked reaction product in which polymer chains of the ionomer are cova-lently connected via molecules of the olefin copolymer.
Upon this reaction the carboxylic acid salt units in the ionomer appear to act as a catalyst. In this reaction no by-products such as water and gases are formed, and thus foaming due to by-products is not observed.
The reaction between the ionomer (A) and the olefin copolymer (B) is conveniently carried out by melt blending the reactants. While the reaction may be carried out in so-lution by dissolving and bringing the reactants in contact to each other in an appropriate solvent, this solution pro-cess requlres a relatively long reaction time and an addi-tional step of solvent removal. Accordingly, we prefer to the melt blending process. The melt blending may be car-ried out in a melt mixer or processing apparatus for ther-moplastic resins at a temperature of from 100 to 300 ~C., preferably from 150 to 280 ~C.
The proportions of the reactants used in the prepara-tion of the crosslinked ionomer are from 90 to 99.5 % by weight, preferably from 92 to 99 % by weight, of the ionomer (A) to from 0.5 to 10 % by weight, preferably from 1 to 8 ~ by weight, of the olefin copolymer (B) having 1 o 2~9~5 epoxy groups in its side chains. With substantially less than 0.5 % by weight of the olefin copolymer (B) having epoxy groups in its side chains based on the total weight of the ionomer (A) and olefin copolymer (B), no appreciable reduction in "luster reappearance" of the crosslinked ionomer, and in turn the final ionomer composition, will be achieved. Whereas use of the olefin copolymer (B) substan-tially in excess of 10 % by weight based on the total weight of the ionomer (A) and olefin copolymer (B) will re-sult in excessive crosslinking, leading to a remarkable re-duction in flowability and moldability of the crosslinked ionomer, and in turn the final ionomer composition.
The olefin-type thermoplastic elastomer (C) used herein comprises an ethylene-a-olefin copolymer rubber (a) and a polyolefin resin (b) as essential ingredients, with the proviso that at least one of the ingredients (a) and (b), normally the ethylene-a-olefin copolymer rubber (a), is partly crosslinked.
The olefin-type thermoplastic elastomer (C) can be a partly crosslinked rubber composition (I) obtained by partly crosslinking a mixture of the ethylene-a-olefin copolymer rubber (a) and the polyolefin resin (b); or a composition obtained by adding a further polyolefin resin (II) to the partly crosslinked rubber composition (I) above; or a composition obtained by adding the polyolefin resin (II) to a a partly crosslinked ethylene-a-olefin copolymer rubber. The material to be partly crosslinked, 1 1 ZOC~39~5 that is the ethylene-a-olefin copolymer rubber or the mix-ture of the ethylene-a-olefin copolymer rubber (a) and the polyolefin resin (b) may be incorporated with a peroxide-noncrosslinkable hydrocarbon rubber (c) and/or a mineral oil softener (d).
More particularly, examples of the olefin-type thermo-plastic elastomer (C) include:
(1) a thermoplastic elastomer composition (I) obtained 0 by dynamic heat treatment of a mixture comprising:
(a) from 20 to 95 parts by weight, preferably from 80 to 30 parts be weight, of an ethylene-a-olefin copolymer rubber, (b) from 5 to 80 parts by weight, preferably from 20 to 70 parts by weight, of a polyolefin resin, and option-ally from 0 to.100 parts by weight,preferably from 5 to 80 parts by weight, based on 100 parts by weight of the total weight of the (a) ~ (b), of at least one component selecled from (c) peroxide-noncrosslinkable hydrocarbon rubbers and (d) mineral oil softeners in the presence of a crosslinking agent;
(2) a composition comprising 30 parts by weight of the thermoplastic elastomer composition (I) above and up to 70 parts by weight of a polyolefin resin (II), the total weight of (b) and [II] in the final composition being up to 12 2~3925 80 parts by weight based on 100 parts by weight of the com-position;
(3) a thermoplastic elastomer composition comprising:
(I~ from 95 to 20 parts by weight of a partly crosslinked ethylene-a-olefin copolymer rubber obtained by dynamic heat treatment of a mixture comprising:
(a) an ethylene-a-olefin copolymer rubber, and from 0 to 100 parts by weight, based on 100 parts by weight of the ethylene-a-olefin copolymer rubber, of at least one component selected from (c) peroxide-noncrosslinkable hydrocarbon rubbers and (d) mineral oil softeners in the presence of a crosslinking agent, and (II) from 5 to 80 parts by weight of a polyolefin resin; and (4) a thermoplastic elastomer composition comprising:
(I) from 80 to 20 parts by weight of a partly crosslinked ethylene-a-olefin copolymer rubber obtained by static heat treatment (for example hot pressing) of a mix-ture comprising:
(a) an ethylene-a-olefin copolymer rubber, and from 0 to 100 parts by weight, based on 100 parts by weight of the ethylene-a-olefin copolymer rubber, of at least one component selected from (c~ peroxide-noncrosslinkable hydrocarbon rubbers and (d) mineral oil softeners in the presence of a crosslinking agent, and 1 3 2~R925 (II) from 20 to 80 parts by weight of a polyolefin resin.
Of these, thermoplastic elastomer compositions (1), 5 (2) and (3) are preferred.
The thermoplastic elastomer (C) used herein should be partly crosslinked. If a noncrosslinked elastomer composi-tion is used, the resulting ionomer composition does not have a satisfactory resistance to heat deformation.
As the ethylene-a-olefin copolymer rubber (a) for preparing the partly crosslinked olefin-type thermoplastic elastomer (C), use can be made of substantially amorphous elastomers derived from ethylene and a-olefin having frorn 3 to 14 carbon atoms, such as ethylene-propylene copolymer rubbers, ethylene-propylene-nonconjugated diene terpolymer or quaternary polymer rubbers, ethylene-butadiene copolyrner rubbers, ethylene-1-butene copolymer rubbers and ethylene-1-butene-nonconjugated diene terpolymer or quaternary poly-mer rubbers. Of these, ethylene-propylene copolymer rub-bers and ethylene-propylene-nonconjugated diene terpolymer rubbers are particularly preferred. Examples of the non-conjugated dienes include, for example, dicyclopentadienes, 1,4-hexadiene, cyclooctadiene, methylenenorbornenes, 5-ethylidene-2-norbornene and 5-vinylnorbornene. Of these, dicyclopentadienes and 5-ethylidene-2-norbornene are pre-ferred. These elastomers may be used alone or in combina-tion.
1 4 2~925 The ethylene a-olefin copolymer rubbers (a) used herein preferably contain units derived from ethylene and a-olefin in such a molar ratio that ethylene units/a-olefin units is from 50/50 to 90/10, and more preferablyfrom 70/30 to 85/15. When the copolymer rubbers (a) con-tain units derived from one or more nonconjugated dienes, in addition to units derived from ethylene and alpha-olefin, a molar ratio of units derived from 1-olefin (ethylene + a-olefin having 3 or more carbon atoms) to units derived from one or more nonconjugated dienes is nor-mally 99/1 to 90/10, and preferably from 97/3 to 94/6.
As the polyolefin resin (b) which is dynamically heat treated with the ethylene/a-olefin copolymer (a), use can be made of resinous high polymer substances including ho-mopolymers of 1-olefins such as ethylene, propylene, butene-1, hexene-1 and 4-methyl-pentene-1, copolymers of at least two 1-olefins and copolymers of 1-olefins and up to 15~ by mole of at least one other copolymerizable monomer, such as ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-methyl acrylate copolymers, ethy-lene-ethyl acrylate copolymers, ethylene-methacrylic acid copolymers and ethylene-methyl methacrylate copolymers.
Of these, polyolefin resins having a melt flow rate of from 0.1 to 50 g/10 min., in particular from 5 to 20 g/10 min., as measured in accordance with ASTM-D-1238-65T
(measured at 190 ~C. in cases of ethylene copolymers and at 1 5 2~925 230 ~C. in cased of propylene copolymers) and having a crystallinity index of at least 40 ~, as measured by X-ray diffractometry, are preferred.
As the polyolefin resin (b), particularly preferred are peroxide-decomposable polyolefin resins having the above-specified melt flow rate and crystallinity. The term "peroxide-decomposable polyolefin resins" means that the polyolefin resins undergo cleavage of polymer chains to some extent to reduce molecular weight thereof and to in-crease in melt flow rate, when kneaded together with a per-oxide under heat. Examples of such peroxide-decomposable polyolefin resins include, for example, isotactic polypropylene and copolymers of propylene with up to 15 mol % of other a-olefins such as propylene-ethylene copolymers, propylene-1-butene copolymers, propylene-1-hexene copoly-mers and propylene-4-methyl-1-pentene copolymers.
Blends of such peroxide-decomposable polyolefin resins with peroxide crosslinkable resins such as low, medium and high density polyethylenes having a density of from 0.910 to 0.940 g/cm3 may also be used as the polyolefin resin (b) in the practice of the invention. The term "peroxide crosslinkable polyolefin resins" means that the polyolefin resins undergo crosslinking of polymer chains to some ex-tent and decrease in melt flow rate when kneaded together with a peroxide under heat.
1 6 26~8925 Examples of the peroxide-noncrosslinkable hydrocarbon rubbers (c), which can be used herein, include, for exam-ple, polyisobutylene rubbers, butyl rubbers, propy-lene/ethylene copolymer rubbers having a propylene content of at least 70 % by mole, propylene-l-butene copolymer rub-bers having a propylene content of at least 70 % by mole and atactic polypropylenes. Of these, polyisobutylene and propylene-l-butene copolymer rubbers are preferred. By t:he term "peroxide-noncrosslinkable hydrocarbon rubbers" is meant that the hydrocarbon rubbers do not undergo crosslinking of polymer chain and do not decrease in melt flow rate even when they are kneaded in the presence of a peroxide under heat.
As the mineral oils (d), use can be made of paraf-finic, naphthenic and aromatic high boiling petroleum frac-tions normally employed in rubber industry for a purpose of weakening intermolecular action of rubbers thereby facili-tating roll processing thereof and promoting dispersion of carbon black or white carbon thereinto, or for a purpose of reducing hardness of vulcanized rubbers thereby enhancing flexibility or elasticity thereof.
As the polyolefin resin [II], which is optionally added to the partly crosslinked rubber composition [I]
after the dynamic heat treatment, use can be made of those hereinbefore described with respect to the polyolefin resin (b), that is, homopolymers of l-olefins such as ethylene, propylene, butene-l, hexene-l and 4-methyl-pentene-1, copolymers of at least two l-olefins and copolymers of 1-1 7 Z~OR925 olefins and up to 15 % by mole of at least one othercopolymerizable monomer, such as ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copoly-mers, ethylene-methacrylic acid copolymers and ethylene-methyl methacrylate copolymers. Of these, polyolefin resins having a melt flow rate of from 5 to 100 g/10 min., in particular from 10 to 50 g/10 min., as measured in ac-cordance with ASTM-D-1238-65T (at 190 ~C., or at 230 ~C. in the case of polymers of propylene), are preferred. In cases wherein both the polyolefin resins (b) and (II) are added during and after the dynamic heat treatment, they rnay be the same or different.
The thermoplastic elastomer (C) may be prepared, for example, by providing a blend comprising from 100 to 20 parts by weight of an ethylene-~-olefin copolymer rubber (a), from 0 to 80 parts by weight of a polyolefin resin (b), and optionally from 0 to 100 parts by weight of a per-oxide-noncross-linkable hydrocarbon rubber (c) and/or min-eral oil softener (d), incorporating the blend with from about 0.05 to 2 % by weight, preferably from 0.1 to 0.5 %
by weight, based on the weight of the blend, of a crosslinking agent and dynamically heat treating the re-sulting mixture to effect the partial crosslinking. Thethermoplastic elastomer so prepared may be incorporated with an additional amount of a polyolefin resin (II), 1 8 Z~R9~5 By the term "dynamic heat treatment of a blend" used herein is meant kneading the blend in molten condition.
The kneading is preferably carried out using a closed appa-ratus under an atmosphere of an inert gas such as nitrogen and carbon dioxide. The kneading temperature is normally from 150 to 280~C., preferably from 170 to 240 ~C., and the kneading time is normally from 1 to 20 minutes, preferably from 1 to 10 minutes.
The crosslinking agents, which can be used herein, in-clude organic peroxides, sulfur, phenolic vulcanizing agents, oximes and polyamines. Of these, organic peroxides and phenolic vulcanizing agents are preferred in view of properties of the resulting thermoplastic elastomers.
Examples of organic peroxides include, for example, dicumyl peroxide, di-tert.-butyl peroxide, 2,5-dimethyl-2,5-bis(tert.-butylperoxy)hexane, 2,5-dimethyl-2,5-bis(tert.-butylperoxy)hexyne-3, 1,3-bis(tert.-butylperoxy-isopropyl)benzene, 1,1-bis(tert.-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis(tert.-butylper-oxy)valerate, dibenzoyl peroxide and tert.-butylperoxy ben-zoate. Of course, bisperoxide compounds, in particular, 1,3-bis(tert.-butylperoxyisopropyl)benzene, is preferred in view of their less ill-smelling and scorch resistant prop-erties.
1 9 2~925 Examples of the phenolic vulcanizing agents include, for example, alkylphenol-formaldehyde resins, triazine-formaldehyde resins and melamine-formaldehyde resins.
The thermoplastic elastomers used herein preferably have a Shore hardness A of not more than 95, preferably form 50 to 95 as measured in accordance with JIS K 7215, MFR of from 1 to 100 g/10 min, preferably from 5 to 70 g/10 min, measured at a temperature of 230 ~C. and under a load of 10 kg, and a flexural modulus of from 200 to 7000 kg/cm2, preferably from 300 to 5000 kg/cm2. Such thermo-plastic elastomers are commercially available under trade names of MILASTOMER~ (supplied by MITSUI Petrochemical Industries Ltd.), THERMOLAN~ (supplied by MITSUBISHI
Petrochemical Co. and Japan Synthetic Rubber Co., Ltd.) and SUMITOMO TPE~ (supplied by SUMITOMO Chemical Co.', Ltd.).
The ionomer composition according to the invention comprises a reaction product of the ethylene copolymer-type ionomer (A) with the olefin copolymer (B) having epoxy groups in its side chains, and from 5 to 200 parts by weight, preferably from 50 to 150 parts by weight, based on 100 parts by weight of said reaction product, of the olefin-type thermoplastic elastomer (C). With substan-tially less than 5 parts by weight of the thermoplasticelastomer (C) based on 100 parts by weight of the reaction product of (A) and (B), the resulting ionomer composition does not have a satisfactory flexibility. Whereas with substantially in excess of 200 parts by weight of the ther-2 o Z~C~3925 moplastic elastomer (C) based on 100 parts by weight of thereaction product of (A) and (B), the resulting ionomer com-position does not have a satisfactory scratch resistance.
Since the crosslinking reaction of the ethylene copolymer-type ionomer (A) with the olefin copolymer (B) having epoxy groups in its side chains is not affected by the presence of the olefin-type thermoplastic elastomer (C), it is possible to melt extrude a blend of the ethylene copolymer-type ionomer (A), the olefin copolymer (B) having epoxy groups in its side chains and the olefin-type thermo-plastic elastomer (C) thereby simultaneously effecting the crosslinking reaction of the ethylene copolymer-type ionomer (A) with the olefin copolymer (B) and the incorpo-ration of the thermoplastic elastomer (C).
Example~
The invention will now be illustrated by the following Examples and Comparative Examples, in which the materials used and the testing methods and evaluations were as fol-lows.
Ionomer 1 having an ethylene content of 97 mole %, a methacrylic acid content of 1 mole % and a zinc methacry-late content of 2 mole %.
Ionomer 2 having an ethylene content of 96 mole %, amethacrylic acid content of 1 mole % and a zinc methacry-late content of 3 mole %.
2 1 Z~925 TPE 1, partly crosslinked olefin-type thermoplastic elastomer (MILASTOMER 8030 B ~, supplied by MITSVI
Petrochemical Industries Ltd.) having an MFR of 0.5 g/10 min measured at 230 ~C. and under a load of 10 kg and a Shore A hardness of 85.
TPE 2, partly crosslinked olefin-type thermoplastic elastomer (MILASTOMER 6030 B ~, supplied by MITSUI
Petrochemical Industries Ltd.) having an MFR of 25 g/10 min measured at 230 ~C. and under a load of 10 kg and a Shore A
hardness of 60.
EGMA, ethylene-glycidyl methacrylate copolymer having a glycidyl methacrylate content of 8 % by weight and an MFR
of 6 g/10 min measured at 190 ~C. and under a load of 2160 g-EVAGMA, ethylene-vinyl acetate-glycidyl methacrylate terpolymer having a vinyl acetate content of 4.5 % by weight, a glycidyl methacrylate content of 8 ~ by weight and an MFR of 6 g/10 min measured at 190 ~C. and under a load of 2160 g.
EnBAGMA, ethylene-n-butyl acrylate-glycidyl methacry-late terpolymer having a n-butyl acrylate content of 7 % by weight, a glycidyl methacrylate content of 10 % by weight and an MFR of 6 g/10 min measured at 190 ~C. and under a load of 2160 g.
22 2~0~925 M.F.R. (melt flow rate) of the ionomer composit-ion was measured in accordance with JIS-K-6710 at a temperature of 190 ~C. and under a load of 2160 g.
5Flexural modulu3 ~as measured on a test pies of a thickness of 2 mm in accordance with ASTM D-747.
Lu~ter reappearance was measured as follows. A T-die extruded and embossed sheet (having a thickness of 0.2 mm) of an ionomer composition was laminated with a 30 times expanded polypropylene foam sheet having a thickness of 2 mm. The laminated sheet was caused to stand in an oven maintained at a temperature of 120 ~C. for a period of 25 hours. At the end of the period, change of appearance of 5 the embossed surface was observed and evaluated according to the following keys: A: no change in appearance, C: yet lustrous again due to loss of emboss; and B: intermediate.
Scratch re~istance was measured as follows. The embossed surface of the laminated test sheet mentioned above was rubbed with a notched side of a coin, and a lia-bility of being impaired of the surface of the test sheet was visually observed and evaluated according to the fol-lowing keys: A: not impaired, C: impaired; and B: interme-diate.
Examples 1 to 6 and Comparative Examples 1 to 4 A mixture of Ionomer 1, TPE 1 and EVAGMA in amountsindicated in Table 1 was extruded through a single screw 2 3 Z~0~925 extruder having a diameter of 40 mm under conditions in-cluding a die temperature of 200 ~C. and a number of screw rotation of 30 rpm to provide pellets. The pellets were extruded through a single screw extruder having a diameter of 65 mm equipped with T-die having a width of 700 mm at a T-die temperature of 200 ~C. to a sheet having a thickness of 0.2 mm, which was then caused to pass through a nip of metallic embossing roll. The embossed sheet was laminated with a 30 times expanded polypropylene foam sheet having a thickness of 2 mm. On the so prepared embossed laminated sheet, "luster reappearance" and scratch resistance were tested. On pellets prepared by the single screw extruder having a diameter of 40 mm, the M. E. R. was measured. The pellets were hot pressed at a temperature of 160 ~C. to provide a test piece having a thickness of 2 mm, on which the flexural modulus was determined.
Results are shown in Table 1.
Example 7 Example 2 was repeated except that the Ionomer 1 was replaced with Ionomer 2. The results are shown in Table 1.
Example 8 Example 2 was repeated except that the TPE 1 was re-placed with TPE 2. The results are shown in Table 1.
Example 9 Example 2 was repeated except that the EVAGMA was re-placed with EGMA. The results are shown in Table 1.
2 4 2(~3925 Example 10 Example 2 was repeated except that the EVAGMA was re-placed with EnBAGMA. The results are shown in Table 1.
Z~Q892S
~ ~ 0 oC~l o X ~ oo o ~n ~ ~ ~o o ~r In X ~ oo o ~ ~ ~ o0 o X O~ OO ~ ~ f~
~
o 0 ~ oa~ ~ m ~ ~ O ~ ~
~ ~ O
~d E~
~ 0 ~ O ~U~
X ~ O ~ O
o 0 ~ O O O
X a~
r~ ~
o a U
u ~ c~
h o U ~ a)~ h E E 1~
~ ~ U
o.
!
-26- 2~9~5 Ul ~ ~ o o o X ~~I o o~
w o 0 ~ o ~ <', cn o ~
X ~ o ~~ ao oo U~
~ cn o ~
X ~o a~ o ~ ~ ~ ~ O
X ~ o ,_1 o ~~ ~ o . ~ o a ~
- ~ ~ ~ V
a) ~,,~ a.~
~ ., o Q ~ 3 ~ ~
X ~ _, ~_~ O JJ ---- V~
X
~ o o c~
o ~ o a~
O
a, ~ ~
3 U (~l C
~ E~ ~ o o - ~ H ~ ~ ~ X
(I~ from 95 to 20 parts by weight of a partly crosslinked ethylene-a-olefin copolymer rubber obtained by dynamic heat treatment of a mixture comprising:
(a) an ethylene-a-olefin copolymer rubber, and from 0 to 100 parts by weight, based on 100 parts by weight of the ethylene-a-olefin copolymer rubber, of at least one component selected from (c) peroxide-noncrosslinkable hydrocarbon rubbers and (d) mineral oil softeners in the presence of a crosslinking agent, and (II) from 5 to 80 parts by weight of a polyolefin resin; and (4) a thermoplastic elastomer composition comprising:
(I) from 80 to 20 parts by weight of a partly crosslinked ethylene-a-olefin copolymer rubber obtained by static heat treatment (for example hot pressing) of a mix-ture comprising:
(a) an ethylene-a-olefin copolymer rubber, and from 0 to 100 parts by weight, based on 100 parts by weight of the ethylene-a-olefin copolymer rubber, of at least one component selected from (c~ peroxide-noncrosslinkable hydrocarbon rubbers and (d) mineral oil softeners in the presence of a crosslinking agent, and 1 3 2~R925 (II) from 20 to 80 parts by weight of a polyolefin resin.
Of these, thermoplastic elastomer compositions (1), 5 (2) and (3) are preferred.
The thermoplastic elastomer (C) used herein should be partly crosslinked. If a noncrosslinked elastomer composi-tion is used, the resulting ionomer composition does not have a satisfactory resistance to heat deformation.
As the ethylene-a-olefin copolymer rubber (a) for preparing the partly crosslinked olefin-type thermoplastic elastomer (C), use can be made of substantially amorphous elastomers derived from ethylene and a-olefin having frorn 3 to 14 carbon atoms, such as ethylene-propylene copolymer rubbers, ethylene-propylene-nonconjugated diene terpolymer or quaternary polymer rubbers, ethylene-butadiene copolyrner rubbers, ethylene-1-butene copolymer rubbers and ethylene-1-butene-nonconjugated diene terpolymer or quaternary poly-mer rubbers. Of these, ethylene-propylene copolymer rub-bers and ethylene-propylene-nonconjugated diene terpolymer rubbers are particularly preferred. Examples of the non-conjugated dienes include, for example, dicyclopentadienes, 1,4-hexadiene, cyclooctadiene, methylenenorbornenes, 5-ethylidene-2-norbornene and 5-vinylnorbornene. Of these, dicyclopentadienes and 5-ethylidene-2-norbornene are pre-ferred. These elastomers may be used alone or in combina-tion.
1 4 2~925 The ethylene a-olefin copolymer rubbers (a) used herein preferably contain units derived from ethylene and a-olefin in such a molar ratio that ethylene units/a-olefin units is from 50/50 to 90/10, and more preferablyfrom 70/30 to 85/15. When the copolymer rubbers (a) con-tain units derived from one or more nonconjugated dienes, in addition to units derived from ethylene and alpha-olefin, a molar ratio of units derived from 1-olefin (ethylene + a-olefin having 3 or more carbon atoms) to units derived from one or more nonconjugated dienes is nor-mally 99/1 to 90/10, and preferably from 97/3 to 94/6.
As the polyolefin resin (b) which is dynamically heat treated with the ethylene/a-olefin copolymer (a), use can be made of resinous high polymer substances including ho-mopolymers of 1-olefins such as ethylene, propylene, butene-1, hexene-1 and 4-methyl-pentene-1, copolymers of at least two 1-olefins and copolymers of 1-olefins and up to 15~ by mole of at least one other copolymerizable monomer, such as ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-methyl acrylate copolymers, ethy-lene-ethyl acrylate copolymers, ethylene-methacrylic acid copolymers and ethylene-methyl methacrylate copolymers.
Of these, polyolefin resins having a melt flow rate of from 0.1 to 50 g/10 min., in particular from 5 to 20 g/10 min., as measured in accordance with ASTM-D-1238-65T
(measured at 190 ~C. in cases of ethylene copolymers and at 1 5 2~925 230 ~C. in cased of propylene copolymers) and having a crystallinity index of at least 40 ~, as measured by X-ray diffractometry, are preferred.
As the polyolefin resin (b), particularly preferred are peroxide-decomposable polyolefin resins having the above-specified melt flow rate and crystallinity. The term "peroxide-decomposable polyolefin resins" means that the polyolefin resins undergo cleavage of polymer chains to some extent to reduce molecular weight thereof and to in-crease in melt flow rate, when kneaded together with a per-oxide under heat. Examples of such peroxide-decomposable polyolefin resins include, for example, isotactic polypropylene and copolymers of propylene with up to 15 mol % of other a-olefins such as propylene-ethylene copolymers, propylene-1-butene copolymers, propylene-1-hexene copoly-mers and propylene-4-methyl-1-pentene copolymers.
Blends of such peroxide-decomposable polyolefin resins with peroxide crosslinkable resins such as low, medium and high density polyethylenes having a density of from 0.910 to 0.940 g/cm3 may also be used as the polyolefin resin (b) in the practice of the invention. The term "peroxide crosslinkable polyolefin resins" means that the polyolefin resins undergo crosslinking of polymer chains to some ex-tent and decrease in melt flow rate when kneaded together with a peroxide under heat.
1 6 26~8925 Examples of the peroxide-noncrosslinkable hydrocarbon rubbers (c), which can be used herein, include, for exam-ple, polyisobutylene rubbers, butyl rubbers, propy-lene/ethylene copolymer rubbers having a propylene content of at least 70 % by mole, propylene-l-butene copolymer rub-bers having a propylene content of at least 70 % by mole and atactic polypropylenes. Of these, polyisobutylene and propylene-l-butene copolymer rubbers are preferred. By t:he term "peroxide-noncrosslinkable hydrocarbon rubbers" is meant that the hydrocarbon rubbers do not undergo crosslinking of polymer chain and do not decrease in melt flow rate even when they are kneaded in the presence of a peroxide under heat.
As the mineral oils (d), use can be made of paraf-finic, naphthenic and aromatic high boiling petroleum frac-tions normally employed in rubber industry for a purpose of weakening intermolecular action of rubbers thereby facili-tating roll processing thereof and promoting dispersion of carbon black or white carbon thereinto, or for a purpose of reducing hardness of vulcanized rubbers thereby enhancing flexibility or elasticity thereof.
As the polyolefin resin [II], which is optionally added to the partly crosslinked rubber composition [I]
after the dynamic heat treatment, use can be made of those hereinbefore described with respect to the polyolefin resin (b), that is, homopolymers of l-olefins such as ethylene, propylene, butene-l, hexene-l and 4-methyl-pentene-1, copolymers of at least two l-olefins and copolymers of 1-1 7 Z~OR925 olefins and up to 15 % by mole of at least one othercopolymerizable monomer, such as ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copoly-mers, ethylene-methacrylic acid copolymers and ethylene-methyl methacrylate copolymers. Of these, polyolefin resins having a melt flow rate of from 5 to 100 g/10 min., in particular from 10 to 50 g/10 min., as measured in ac-cordance with ASTM-D-1238-65T (at 190 ~C., or at 230 ~C. in the case of polymers of propylene), are preferred. In cases wherein both the polyolefin resins (b) and (II) are added during and after the dynamic heat treatment, they rnay be the same or different.
The thermoplastic elastomer (C) may be prepared, for example, by providing a blend comprising from 100 to 20 parts by weight of an ethylene-~-olefin copolymer rubber (a), from 0 to 80 parts by weight of a polyolefin resin (b), and optionally from 0 to 100 parts by weight of a per-oxide-noncross-linkable hydrocarbon rubber (c) and/or min-eral oil softener (d), incorporating the blend with from about 0.05 to 2 % by weight, preferably from 0.1 to 0.5 %
by weight, based on the weight of the blend, of a crosslinking agent and dynamically heat treating the re-sulting mixture to effect the partial crosslinking. Thethermoplastic elastomer so prepared may be incorporated with an additional amount of a polyolefin resin (II), 1 8 Z~R9~5 By the term "dynamic heat treatment of a blend" used herein is meant kneading the blend in molten condition.
The kneading is preferably carried out using a closed appa-ratus under an atmosphere of an inert gas such as nitrogen and carbon dioxide. The kneading temperature is normally from 150 to 280~C., preferably from 170 to 240 ~C., and the kneading time is normally from 1 to 20 minutes, preferably from 1 to 10 minutes.
The crosslinking agents, which can be used herein, in-clude organic peroxides, sulfur, phenolic vulcanizing agents, oximes and polyamines. Of these, organic peroxides and phenolic vulcanizing agents are preferred in view of properties of the resulting thermoplastic elastomers.
Examples of organic peroxides include, for example, dicumyl peroxide, di-tert.-butyl peroxide, 2,5-dimethyl-2,5-bis(tert.-butylperoxy)hexane, 2,5-dimethyl-2,5-bis(tert.-butylperoxy)hexyne-3, 1,3-bis(tert.-butylperoxy-isopropyl)benzene, 1,1-bis(tert.-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis(tert.-butylper-oxy)valerate, dibenzoyl peroxide and tert.-butylperoxy ben-zoate. Of course, bisperoxide compounds, in particular, 1,3-bis(tert.-butylperoxyisopropyl)benzene, is preferred in view of their less ill-smelling and scorch resistant prop-erties.
1 9 2~925 Examples of the phenolic vulcanizing agents include, for example, alkylphenol-formaldehyde resins, triazine-formaldehyde resins and melamine-formaldehyde resins.
The thermoplastic elastomers used herein preferably have a Shore hardness A of not more than 95, preferably form 50 to 95 as measured in accordance with JIS K 7215, MFR of from 1 to 100 g/10 min, preferably from 5 to 70 g/10 min, measured at a temperature of 230 ~C. and under a load of 10 kg, and a flexural modulus of from 200 to 7000 kg/cm2, preferably from 300 to 5000 kg/cm2. Such thermo-plastic elastomers are commercially available under trade names of MILASTOMER~ (supplied by MITSUI Petrochemical Industries Ltd.), THERMOLAN~ (supplied by MITSUBISHI
Petrochemical Co. and Japan Synthetic Rubber Co., Ltd.) and SUMITOMO TPE~ (supplied by SUMITOMO Chemical Co.', Ltd.).
The ionomer composition according to the invention comprises a reaction product of the ethylene copolymer-type ionomer (A) with the olefin copolymer (B) having epoxy groups in its side chains, and from 5 to 200 parts by weight, preferably from 50 to 150 parts by weight, based on 100 parts by weight of said reaction product, of the olefin-type thermoplastic elastomer (C). With substan-tially less than 5 parts by weight of the thermoplasticelastomer (C) based on 100 parts by weight of the reaction product of (A) and (B), the resulting ionomer composition does not have a satisfactory flexibility. Whereas with substantially in excess of 200 parts by weight of the ther-2 o Z~C~3925 moplastic elastomer (C) based on 100 parts by weight of thereaction product of (A) and (B), the resulting ionomer com-position does not have a satisfactory scratch resistance.
Since the crosslinking reaction of the ethylene copolymer-type ionomer (A) with the olefin copolymer (B) having epoxy groups in its side chains is not affected by the presence of the olefin-type thermoplastic elastomer (C), it is possible to melt extrude a blend of the ethylene copolymer-type ionomer (A), the olefin copolymer (B) having epoxy groups in its side chains and the olefin-type thermo-plastic elastomer (C) thereby simultaneously effecting the crosslinking reaction of the ethylene copolymer-type ionomer (A) with the olefin copolymer (B) and the incorpo-ration of the thermoplastic elastomer (C).
Example~
The invention will now be illustrated by the following Examples and Comparative Examples, in which the materials used and the testing methods and evaluations were as fol-lows.
Ionomer 1 having an ethylene content of 97 mole %, a methacrylic acid content of 1 mole % and a zinc methacry-late content of 2 mole %.
Ionomer 2 having an ethylene content of 96 mole %, amethacrylic acid content of 1 mole % and a zinc methacry-late content of 3 mole %.
2 1 Z~925 TPE 1, partly crosslinked olefin-type thermoplastic elastomer (MILASTOMER 8030 B ~, supplied by MITSVI
Petrochemical Industries Ltd.) having an MFR of 0.5 g/10 min measured at 230 ~C. and under a load of 10 kg and a Shore A hardness of 85.
TPE 2, partly crosslinked olefin-type thermoplastic elastomer (MILASTOMER 6030 B ~, supplied by MITSUI
Petrochemical Industries Ltd.) having an MFR of 25 g/10 min measured at 230 ~C. and under a load of 10 kg and a Shore A
hardness of 60.
EGMA, ethylene-glycidyl methacrylate copolymer having a glycidyl methacrylate content of 8 % by weight and an MFR
of 6 g/10 min measured at 190 ~C. and under a load of 2160 g-EVAGMA, ethylene-vinyl acetate-glycidyl methacrylate terpolymer having a vinyl acetate content of 4.5 % by weight, a glycidyl methacrylate content of 8 ~ by weight and an MFR of 6 g/10 min measured at 190 ~C. and under a load of 2160 g.
EnBAGMA, ethylene-n-butyl acrylate-glycidyl methacry-late terpolymer having a n-butyl acrylate content of 7 % by weight, a glycidyl methacrylate content of 10 % by weight and an MFR of 6 g/10 min measured at 190 ~C. and under a load of 2160 g.
22 2~0~925 M.F.R. (melt flow rate) of the ionomer composit-ion was measured in accordance with JIS-K-6710 at a temperature of 190 ~C. and under a load of 2160 g.
5Flexural modulu3 ~as measured on a test pies of a thickness of 2 mm in accordance with ASTM D-747.
Lu~ter reappearance was measured as follows. A T-die extruded and embossed sheet (having a thickness of 0.2 mm) of an ionomer composition was laminated with a 30 times expanded polypropylene foam sheet having a thickness of 2 mm. The laminated sheet was caused to stand in an oven maintained at a temperature of 120 ~C. for a period of 25 hours. At the end of the period, change of appearance of 5 the embossed surface was observed and evaluated according to the following keys: A: no change in appearance, C: yet lustrous again due to loss of emboss; and B: intermediate.
Scratch re~istance was measured as follows. The embossed surface of the laminated test sheet mentioned above was rubbed with a notched side of a coin, and a lia-bility of being impaired of the surface of the test sheet was visually observed and evaluated according to the fol-lowing keys: A: not impaired, C: impaired; and B: interme-diate.
Examples 1 to 6 and Comparative Examples 1 to 4 A mixture of Ionomer 1, TPE 1 and EVAGMA in amountsindicated in Table 1 was extruded through a single screw 2 3 Z~0~925 extruder having a diameter of 40 mm under conditions in-cluding a die temperature of 200 ~C. and a number of screw rotation of 30 rpm to provide pellets. The pellets were extruded through a single screw extruder having a diameter of 65 mm equipped with T-die having a width of 700 mm at a T-die temperature of 200 ~C. to a sheet having a thickness of 0.2 mm, which was then caused to pass through a nip of metallic embossing roll. The embossed sheet was laminated with a 30 times expanded polypropylene foam sheet having a thickness of 2 mm. On the so prepared embossed laminated sheet, "luster reappearance" and scratch resistance were tested. On pellets prepared by the single screw extruder having a diameter of 40 mm, the M. E. R. was measured. The pellets were hot pressed at a temperature of 160 ~C. to provide a test piece having a thickness of 2 mm, on which the flexural modulus was determined.
Results are shown in Table 1.
Example 7 Example 2 was repeated except that the Ionomer 1 was replaced with Ionomer 2. The results are shown in Table 1.
Example 8 Example 2 was repeated except that the TPE 1 was re-placed with TPE 2. The results are shown in Table 1.
Example 9 Example 2 was repeated except that the EVAGMA was re-placed with EGMA. The results are shown in Table 1.
2 4 2(~3925 Example 10 Example 2 was repeated except that the EVAGMA was re-placed with EnBAGMA. The results are shown in Table 1.
Z~Q892S
~ ~ 0 oC~l o X ~ oo o ~n ~ ~ ~o o ~r In X ~ oo o ~ ~ ~ o0 o X O~ OO ~ ~ f~
~
o 0 ~ oa~ ~ m ~ ~ O ~ ~
~ ~ O
~d E~
~ 0 ~ O ~U~
X ~ O ~ O
o 0 ~ O O O
X a~
r~ ~
o a U
u ~ c~
h o U ~ a)~ h E E 1~
~ ~ U
o.
!
-26- 2~9~5 Ul ~ ~ o o o X ~~I o o~
w o 0 ~ o ~ <', cn o ~
X ~ o ~~ ao oo U~
~ cn o ~
X ~o a~ o ~ ~ ~ ~ O
X ~ o ,_1 o ~~ ~ o . ~ o a ~
- ~ ~ ~ V
a) ~,,~ a.~
~ ., o Q ~ 3 ~ ~
X ~ _, ~_~ O JJ ---- V~
X
~ o o c~
o ~ o a~
O
a, ~ ~
3 U (~l C
~ E~ ~ o o - ~ H ~ ~ ~ X
Claims (4)
1. An ionomer composition which comprises a reaction product of from 90 to 99.5 % by weight of an ethylene copolymer ionomer (A) comprising ethylene units and unsaturated carboxylic acid salt units with from 0.5 to 10%
by weight of an olefin copolymer (B) having epoxy groups in its side chains, and from 5 to 200 parts by weight, based on 100 parts by weight of said reaction product, of an olefin thermoplastic elastomer (C) comprising an ethylene .alpha.-olefin copolymer rubber (a) and a polyolefin resin (b), at least one of (a) and (b) being partly crosslinked.
by weight of an olefin copolymer (B) having epoxy groups in its side chains, and from 5 to 200 parts by weight, based on 100 parts by weight of said reaction product, of an olefin thermoplastic elastomer (C) comprising an ethylene .alpha.-olefin copolymer rubber (a) and a polyolefin resin (b), at least one of (a) and (b) being partly crosslinked.
2. The polymer composition according to claim 1 wherein said ethylene copolymer-type ionomer (A) is obtained by neutralizing from 10 to 90 % of carboxylic groups of an ethylene copolymer comprising ethylene units, unsaturated carboxylic acid units and optionally unsaturated carboxylic acid ester units with metallic ions having a valency of from 1 to 3.
3. The polymer composition according to claim 1 wherein said olefin copolymer (B) having epoxy groups in its side chains is a copolymer of at least one .alpha.-olefin with at least one ethylenically unsaturated glycidyl compound selected from glycidyl acrylate, glycidyl methacrylate and ethylenically unsaturated glycidyl ethers.
4. The polymer composition according to claim 1 wherein said olefin-type thermoplastic elastomer (C) comprises:
[I] from 100 to 30 parts by weight of a partly cross-linked rubber composition obtained by dynamic heat treatment of a mixture comprising:
(a) from 20 to 95 parts by weight of an ethylene-.alpha.-olefin copolymer rubber, (b) from 5 to 80 parts by weight of a polyolefin resin, the total weight of the (a) + (b) being 100 parts by weight, and from 5 to 80 parts by weight of at least one component selected from (c) peroxide-noncrosslinkable hydrocarbon rubbers and (d) mineral oil softeners in the presence of a crosslinking agent, and [II] from 0 to 70 parts by weight of a polyolefin resin, the total weight of (b) and [II] in the elastomer (C) being from 5 to 80 parts by weight based on 100 parts by weight of the elastomer (C).
[I] from 100 to 30 parts by weight of a partly cross-linked rubber composition obtained by dynamic heat treatment of a mixture comprising:
(a) from 20 to 95 parts by weight of an ethylene-.alpha.-olefin copolymer rubber, (b) from 5 to 80 parts by weight of a polyolefin resin, the total weight of the (a) + (b) being 100 parts by weight, and from 5 to 80 parts by weight of at least one component selected from (c) peroxide-noncrosslinkable hydrocarbon rubbers and (d) mineral oil softeners in the presence of a crosslinking agent, and [II] from 0 to 70 parts by weight of a polyolefin resin, the total weight of (b) and [II] in the elastomer (C) being from 5 to 80 parts by weight based on 100 parts by weight of the elastomer (C).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19490/1989 | 1989-01-31 | ||
| JP1019490A JP2521807B2 (en) | 1989-01-31 | 1989-01-31 | Ionomer composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2008925A1 CA2008925A1 (en) | 1990-07-31 |
| CA2008925C true CA2008925C (en) | 1997-12-23 |
Family
ID=12000802
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002008925A Expired - Fee Related CA2008925C (en) | 1989-01-31 | 1990-01-30 | Ionomer composition |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4968752A (en) |
| EP (1) | EP0382401B1 (en) |
| JP (1) | JP2521807B2 (en) |
| CA (1) | CA2008925C (en) |
| DE (1) | DE69007650T2 (en) |
Families Citing this family (43)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5206294A (en) * | 1991-11-06 | 1993-04-27 | E. I. Du Pont De Nemours And Company | Thermoplastic polymer alloy composition |
| JP3064090B2 (en) * | 1992-02-17 | 2000-07-12 | 住友ゴム工業株式会社 | Golf ball |
| US5223573A (en) * | 1992-02-28 | 1993-06-29 | General Electric Company | PC/ABS blends exhibiting reduced gloss |
| US5284489A (en) * | 1992-08-19 | 1994-02-08 | United States Surgical Corporation | Filament fabricated from a blend of ionomer resin and nonionic thermoplastic resin |
| JP2709562B2 (en) * | 1993-07-02 | 1998-02-04 | 住友ゴム工業株式会社 | Golf ball |
| US5631328A (en) * | 1993-10-27 | 1997-05-20 | Chevron Chemical Company | Low-haze ionomers of copolymers of alpha-olefins, carboxylic acid esters, and optional comonomers, and processes for making and acidifying these ionomers |
| US5721314A (en) * | 1993-12-07 | 1998-02-24 | E. I. Du Pont De Nemours And Company | Thermoformable thermoplastic polymer alloy compositions |
| JP3351081B2 (en) * | 1993-12-15 | 2002-11-25 | ジェイエスアール株式会社 | Thermoplastic elastomer composition |
| US5885172A (en) | 1997-05-27 | 1999-03-23 | Acushnet Company | Multilayer golf ball with a thin thermoset outer layer |
| US5741572A (en) * | 1995-02-17 | 1998-04-21 | Lexmark International, Inc. | Heat fixing paper or sheet |
| US6210294B1 (en) | 1999-05-14 | 2001-04-03 | Acushnet Company | Polyurethane golf ball with improved resiliency |
| US7015300B2 (en) | 1995-06-07 | 2006-03-21 | Acushnet Company | Multilayered golf ball and composition |
| DE19610415A1 (en) * | 1996-03-16 | 1997-09-18 | Schulman A Gmbh | Thermoplastic molding composition, process for its production and its use |
| US5753767A (en) * | 1996-12-13 | 1998-05-19 | Armstrong World Industries, Inc. | Polymer composition suitable as resilient flooring or welding rod |
| US20050070377A1 (en) * | 1997-05-27 | 2005-03-31 | Christopher Cavallaro | Thin-layer-covered multilayer golf ball |
| US6913547B2 (en) | 1997-05-27 | 2005-07-05 | Acushnet Company | Thin-layer-covered multilayer golf ball |
| US6486261B1 (en) | 1998-12-24 | 2002-11-26 | Acushnet Company | Thin-layer-covered golf ball with improved velocity |
| US6634964B2 (en) | 1997-05-27 | 2003-10-21 | Acushnet Company | Initial velocity dual core golf ball |
| US6849006B2 (en) | 1997-05-27 | 2005-02-01 | Acushnet Company | Thin, thermoset, polyurethane-covered golf ball with a dual core |
| US6288156B1 (en) | 1997-09-01 | 2001-09-11 | E. I. Du Pont De Nemours And Company | Calenderable thermoplastic polymer compositions |
| AU8914498A (en) * | 1997-09-01 | 1999-03-22 | Performance Materials Na, Inc. | Thermoplastic polymer compositions |
| US6217982B1 (en) * | 1997-10-10 | 2001-04-17 | E. I. Du Pont De Nemours And Company | Thermoplastic polymer alloy composition |
| US6998445B2 (en) | 1998-03-26 | 2006-02-14 | Acushnet Company | Low compression, resilient golf balls with rubber core |
| US6207761B1 (en) | 1999-03-18 | 2001-03-27 | A. Schulman, Inc. | Ionomer/rubber/polyolefin blend and uses thereof |
| US6392002B1 (en) | 1999-05-14 | 2002-05-21 | Acushnet Company | Urethane golf ball |
| KR100353066B1 (en) | 1999-12-31 | 2002-09-18 | 현대자동차주식회사 | Thermoplastic resin composition |
| JP4705711B2 (en) * | 2000-07-11 | 2011-06-22 | 三井・デュポンポリケミカル株式会社 | Ionomer composition and use thereof |
| EP1454952B1 (en) * | 2001-06-28 | 2006-08-16 | JSR Corporation | Olefinic thermoplastic elastomer, process for production thereof, olefinic thermoplastic elastomer compositions, process for producing the same and moldings thereof |
| DE60325646D1 (en) * | 2003-02-07 | 2009-02-12 | Mitsui Du Pont Polychemical | THERMOPLASTIC RESIN COMPOSITION AND MANUFACTURING METHOD THEREFOR |
| US20080057302A1 (en) * | 2003-10-09 | 2008-03-06 | Jsr Corporation | Elastomer Films And Process For Production Thereof |
| US20060100380A1 (en) * | 2004-11-05 | 2006-05-11 | Delphi Technologies, Inc. | Slush moldable thermoplastic polyolefin formulation for interior skin |
| WO2010051523A1 (en) * | 2008-10-31 | 2010-05-06 | E. I. Du Pont De Nemours And Company | High-clarity ionomer compositions and articles comprising the same |
| BRPI0918686B8 (en) | 2008-12-30 | 2022-07-05 | Du Pont | COMPOSITION, ARTICLE AND ARTICLE PREPARED BY INJECTION MOLDING |
| JP5587336B2 (en) * | 2008-12-31 | 2014-09-10 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Ionomer composition with low haze and high waterproofness and article containing the same |
| TW201109350A (en) * | 2009-07-31 | 2011-03-16 | Du Pont | Cross-linkable encapsulants for photovoltaic cells |
| US8609980B2 (en) * | 2010-07-30 | 2013-12-17 | E I Du Pont De Nemours And Company | Cross-linkable ionomeric encapsulants for photovoltaic cells |
| GB2505617A (en) * | 2011-05-28 | 2014-03-05 | Robert Kasowski | Flame retardant with compositions |
| CN107324125B (en) * | 2017-08-14 | 2020-06-12 | 江苏金佰纳建筑装配有限公司 | Building cable pay-off rack |
| US12157036B2 (en) | 2023-02-10 | 2024-12-03 | Acushnet Company | Multi-layer golf balls with increased interlayer adhesion |
| US12097408B2 (en) | 2023-02-10 | 2024-09-24 | Acushnet Company | Multi-layer golf balls with increased interlayer adhesion |
| US12515106B2 (en) | 2023-02-10 | 2026-01-06 | Acushnet Company | Multi-layer golf balls with increased interlayer adhesion |
| US12420147B2 (en) | 2023-02-10 | 2025-09-23 | Acushnet Company | Multi-layer golf balls with improved interlayer adhesion |
| US12515107B2 (en) | 2023-11-15 | 2026-01-06 | Acushnet Company | Multi-layer golf balls with in-situ adhesion promoter |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5989346A (en) * | 1982-11-12 | 1984-05-23 | Sumitomo Naugatuck Co Ltd | Thermoplastic resin composition |
| JPH066656B2 (en) * | 1984-07-27 | 1994-01-26 | 三井石油化学工業株式会社 | Polymer composition |
| JPS6136347A (en) * | 1984-07-27 | 1986-02-21 | Du Pont Mitsui Polychem Co Ltd | Polymeric composition |
| JPH06839B2 (en) * | 1985-12-17 | 1994-01-05 | 昭和電工株式会社 | Crosslinkable composition |
| CA1296821C (en) * | 1986-11-17 | 1992-03-03 | Lawrence Clark | Dynamically crosslinked thermoplastic elastomer |
| US4898911A (en) * | 1986-11-20 | 1990-02-06 | Kanegafuchi Kagaku Kogyo Kabushiki | Resin composition |
| JPS63165448A (en) * | 1986-12-26 | 1988-07-08 | Kanegafuchi Chem Ind Co Ltd | Resin composition |
| JPS649254A (en) * | 1987-06-30 | 1989-01-12 | Nippon Petrochemicals Co Ltd | Polypropylene resin composition and its production |
-
1989
- 1989-01-31 JP JP1019490A patent/JP2521807B2/en not_active Expired - Fee Related
-
1990
- 1990-01-29 US US07/471,940 patent/US4968752A/en not_active Expired - Lifetime
- 1990-01-30 CA CA002008925A patent/CA2008925C/en not_active Expired - Fee Related
- 1990-01-31 EP EP90301027A patent/EP0382401B1/en not_active Expired - Lifetime
- 1990-01-31 DE DE69007650T patent/DE69007650T2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02202531A (en) | 1990-08-10 |
| EP0382401B1 (en) | 1994-03-30 |
| EP0382401A2 (en) | 1990-08-16 |
| US4968752A (en) | 1990-11-06 |
| EP0382401A3 (en) | 1991-01-30 |
| CA2008925A1 (en) | 1990-07-31 |
| JP2521807B2 (en) | 1996-08-07 |
| DE69007650T2 (en) | 1994-07-21 |
| DE69007650D1 (en) | 1994-05-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2008925C (en) | Ionomer composition | |
| JP2886107B2 (en) | Thermoplastic elastomer sheet molding | |
| KR100353066B1 (en) | Thermoplastic resin composition | |
| KR100660494B1 (en) | Thermoplastic Elastomer Composition | |
| EP0738756B1 (en) | Thermoplastic elastomer composition | |
| EP0382849B1 (en) | Polymer composition | |
| WO2002028957A1 (en) | Engineered polyolefin materials with enhanced surface durability | |
| JP2001280555A (en) | Multi-layer hose for automotive cooling system | |
| JPH11124440A (en) | Thermoplastic elastomer | |
| KR102518984B1 (en) | A composition comprising carbon fibers and at least one thermoplastic polyolefin elastomer | |
| JP3333251B2 (en) | Olefin resin composition | |
| JPH0446296B2 (en) | ||
| JPH066656B2 (en) | Polymer composition | |
| US5602203A (en) | Olefin resin composition | |
| EP1040162B1 (en) | Thermoplastic polymer compositions | |
| EP1963426B1 (en) | Thermoplastic vulcanizate adhesive compositions | |
| JP3274181B2 (en) | Polymer composition and method for producing the same | |
| JP4130105B2 (en) | Resin composition for molding and molded body | |
| US6407172B1 (en) | Thermoplastic polymer compositions | |
| JP4314184B2 (en) | Ethylene terpolymer and propylene resin composition | |
| JPH11279344A (en) | Resin composition for blow molding | |
| CA1339967C (en) | Polymer composition | |
| JP2003176388A (en) | Thermoplastic elastomer composition and method for producing the same | |
| JPH0688366B2 (en) | Laminate | |
| JPH0826195B2 (en) | polymer composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |